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Coatings 08 00014
Coatings 08 00014
Article
Composition and Structure Evolution of Bi2O3
Coatings as Efficient Photocatalysts
Lijun Cheng 1 , Liang Hao 1, * and Yun Lu 2 ID
1 Tianjin Key Laboratory of Integrated Design and On-line Monitoring for Light Industry & Food Machinery
and Equipment, College of Mechanical Engineering, Tianjin University of Science & Technology,
Tianjin 300222, China; chenglijun@tust.edu.cn
2 College of Mechanical Engineering & Graduate School, Chiba University, Chiba 263-8522, Japan;
luyun@faculty.chiba-u.jp
* Correspondence: haoliang@tust.edu.cn; Tel.: +86-22-6060-0692
Abstract: To overcome the recovery disadvantages of Bi2 O3 photocatalyst in the form of powder,
Bi2 O3 photocatalyst coatings were developed via a ball milling, followed by the calcination method.
The composition and structure evolution rules of the as-synthesized samples were analyzed based
on XRD (X-ray powder diffraction) patterns and SEM (scanning electron microscope) observations.
XPS (X-ray photoelectron spectroscopy) and UV-Vis (Ultraviolet-visible) spectra were also employed
to characterize the samples. The results showed that monoclinic Bi2 O3 coatings were obtained after
sintering Bi coatings at 673 or 773 K for 2 h, while calcination at a higher temperature and for a
longer time resulted in monoclinic and triclinic mixed-phase Bi2 O3 coatings. Bi2 O3 coatings with a
radial growth structure assembled by nanosheets could be realized at a lower temperature lasting
for a longer time, while sintering at a higher temperature with relatively short oxidation time led to
tangential growth structure. Photodegradation of malachite green solution under simulated solar
irradiation for 180 min showed that the largest degradation efficiency of 91.49% was achieved over
the photocatalyst coatings calcined at 873 K for 5 h. Additionally, the degradation efficiency was
maintained above 80% even after three cycles.
1. Introduction
Nowadays, environmental pollution and energy crisis cause extremely severe and destructive
effects for human health and society development. Fortunately, photocatalysis technology appears
as an efficient, economical, and environmental friendly technology, which can be applied in
environmental remediation, as well as solar energy conversion, since it was discovered in 1972 [1–3].
To date, various types of semiconductor photocatalysts have been explored, especially the
TiO2 -based photocatalysts which are always being ranked as the most researched ones [4–6].
However, their applications are retarded by low ultilization efficiency for solar light absorption
or a high recombination of charge carriers, thus making development of photocatalysts with visible
light responsive ability indispensable. Recently, bismuth-based semiconductor photocatalysts have
been demonstrated to exhibit superior photocatalytic activity under visible-light irradiation, and the
interest in bismuth-based semiconductors is continuing to grow [7–12].
In order to push the applications of photocatalysts in practical industry fields, such as waste water
treatment, the dispersity, recovery, and repeatability of the photocatalysts are of great significance.
Yet, it is difficult to realize such an objective with photocatalysts in powder form, which impels the
pursuit of a valid method to achieve improved recovery properties of photocatalysts. Among various
approaches, immobilizing photocatalyst particles onto some kind of supporter is effective at achieving
such an objective. Hence, ZnO nanoparticles immobilized montmorillonite [13], Nano-TiO2 -loaded
activated carbon fiber [14], TiO2 -montmorillonite composite [15], acid-treated vermiculite supported
TiO2 [16], TiO2 supported silica nanolayers [17], TiO2 /HZSM-5 composite [18], and Ag–TiO2
photocatalyst supported on glass fiber [19] were synthesized to improve the dispersity of photocatalyst
particles and, consequently, photocatalytic performances.
With regard to bismuth-based loaded photocatalysts, there have been some reports as well.
Wang et al. [20] synthesized Bi2 O3 /HZSM-5 composite photocatalysts via a facile ion-exchange
method. The results showed that the Bi2 O3 /HZSM-5 composite photocatalyst acquires the highest
photocatalytic activity for rhodamine B degradation at the optimal loading with 18 wt % Bi2 O3
and proposed the synergistic effect between HZSM-5 and Bi2 O3 , namely, the special structure of
HZSM-5 increased the number of the active sites to adsorb more dye molecules and photodegraded
them on the Bi2 O3 photocatalyst. Zhang et al. [21] immobilized the Bi2 WO6 /Bi2 O3 composite onto
the polyurethane sponge and obtained enhanced photocatalytic activity and reusability towards
rhodamine B degradation. Jiao et al. [22] prepared the Mg/Al layered double hydroxide loaded
Pd(II)-Bi2 O3 via impregnation and calcination technique. The results displayed that the sample
possessed high crystallinity, large specific surface area, and broad absorption in the visible region,
which contributed to its excellent photocatalytic activity for methylene blue degradation.
To overcome the recycle problem thoroughly, Al2 O3 balls with an average diameter of 1 mm
were used as the substrate to prepare bismuth-based photocatalyst coatings. Metallic Bi powder was
employed as the starting material to be coated on the surface of Al2 O3 balls via a mechanical ball milling
method, and Bi2 O3 coatings were obtained by sintering the above Bi coatings. The composition and
structure evolution rules of the as-synthesized samples were analyzed based on XRD (X-ray powder
diffraction) patterns and SEM (scanning electron microscope) observations. The optical properties and
the photo-degradation performances of the samples were also studied with the aim of providing a
new type of bismuth-based semiconductor photocatalyst coating that is applicable to practical water
cleaning or other contaminants disposal.
2. Experimental
2.2. Characterization
X-ray diffraction (XRD) analysis was performed on a Bruker D8 ADVANCE unit (Bruker, Billerica,
MA, USA) using Cu Kα radiation to identify the crystalline phases of the coatings. The surface and
cross-section morphologies of the coatings were observed by scanning electronic microscopy (SEM) on
a Hitachi S-4800 microscope (Hitachi, Tokyo, Japan). The element valence state of Bi was analyzed
with X-ray photoelectron spectroscopy (XPS) on a Thermo ESCALAB 250Xi energy spectrometer
(Thermo Fisher Scientific, Waltham, MA, USA). The UV-Vis diffuse reflectance spectra of the coatings
were recorded on a Lambda 750S UV/VIS/NIR spectrometer (PerkinElmer, Waltham, MA, USA).
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Coatings 2018, 8, 14 3 of 10
spectra of the coatings were recorded on a Lambda 750S UV/VIS/NIR spectrometer (PerkinElmer,
Waltham, MA, USA). Additionally, the absorbance of malachite green (MG) aqueous solution was
tested with a the
Additionally, 722 absorbance
Vis spectrophotometer
of malachite (Sunny Optical
green (MG) Technology
aqueous (Group)
solution Company
was tested with aLimited,
722 Vis
Yuyao, China).
spectrophotometer (Sunny Optical Technology (Group) Company Limited, Yuyao, China).
2.3. Photocatalytic Activity
2.3. Photocatalytic Activity
The photocatalytic
The photocatalytic activities
activities of
of the
the coatings
coatings were
were investigated
investigated byby photodegradation
photodegradation of
of MG
MG
solution with
solution with concentration
concentration of
of 10
10 mg/L,
mg/L, which was performed
which was performed inin aa CEL-LAB500
CEL‐LAB500 Photocatalytic
Photocatalytic
Reactor from CEAULIGHT (Beijing, China). In detail, 0.1 g coatings were dispersed in 50 mL MG
Reactor from CEAULIGHT (Beijing, China). In detail, 0.1 g coatings were dispersed in 50 mL MG
Then, 500 W Xe lamp (light density was 75% ± 5% mW/cm2 ) was turned on to carry out
solution. Then, 500 W Xe lamp (light density was 75% ± 5% mW/cm²) was turned on to carry out the
solution.
degradation experiment. During the reaction period, certain amount of MG solution was taken out,
the degradation experiment. During the reaction period, certain amount of MG solution was taken
centrifuged to separate the photocatalyst, and the residual MG concentration was analyzed by the
out, centrifuged to separate the photocatalyst, and the residual MG concentration was analyzed by the
spectrophotometer at regular intervals.
spectrophotometer at regular intervals.
Figure 1.
Figure 1. XRD
XRD patterns
patterns of
of the
the as-prepared
as‐prepared coatings:
coatings: (a)
(a) BC-673-2,
BC‐673‐2, BC-673-5,
BC‐673‐5, BC-673-10,
BC‐673‐10, BC-773-2,
BC‐773‐2,
BC‐773‐5, BC‐773‐10; (b) BC‐873‐2, BC‐873‐5, BC‐873‐10, BC‐973‐2, BC‐973‐5, BC‐973‐10.
BC-773-5, BC-773-10; (b) BC-873-2, BC-873-5, BC-873-10, BC-973-2, BC-973-5, BC-973-10.
3.2. Microstructure Evolution of the Coatings
3.2. Microstructure Evolution of the Coatings
Figure 2a shows the surface and cross‐section SEM images of initial Bi coatings. It could be found
Figure 2a shows the surface and cross-section SEM images of initial Bi coatings. It could be
that continuous Bi coatings were formed by coalescence of the discrete islands on Al
found that continuous Bi coatings were formed by coalescence of the discrete islands on 2O3 ball after
Al2 O3 ball
mechanical ball milling at 290 rpm for 10 h. The surface of Bi coatings was relatively smooth and the
after mechanical ball milling at 290 rpm for 10 h. The surface of Bi coatings was relatively smooth
Coatings 2018, 8, 14 4 of 10
Coatings 2018, 1, 14 4 of 10
connection trace was obvious. From the cross‐section image, one can see Bi coatings with average
and the connection trace was obvious. From the cross-section image, one can see Bi coatings with
thickness
averageof thickness
30 μm of
were obtained.
30 µm After After
were obtained. the Bi
the coatings
Bi coatingswere
were thermally oxidized
thermally oxidized at different
at different
temperature for different time, a series of Bi
temperature for different time, a series of Bi22O
O33 coatings with harsh surface derived from distinctly
coatings with harsh surface derived from distinctly
different
different oxidation
oxidation degree
degree weresynthesized.
were synthesized. As
As a
a typical
typical example,
example, the micromorphologies
the micromorphologies of the
of the
BC-873-5 sample are displayed in Figure
BC‐873‐5 sample are displayed in Figure 2b. 2b.
(a) (b)
Figure 2. The surface and cross‐section morphologies of (a) Bi coatings and (b) BC‐873‐5.
Figure 2. The surface and cross-section morphologies of (a) Bi coatings and (b) BC-873-5.
To clarify the microstructure transformation of the Bi 2O3 coatings with calcination temperature
To clarify the microstructure transformation of the Bi2 O3 coatings with calcination temperature
and and
time, the high‐resolution SEM images of the coatings
time, the high-resolution SEM images of the coatings are revealed are revealed
in Figurein Figure
3. When the3. BiWhen the Bi
coatings
coatings
werewere oxidized
oxidized at 673 Kat for
673 K Bifor
2 h, 2 h, Bi2O3 crystals grew into thin nanosheets along the radial
2 O3 crystals grew into thin nanosheets along the radial direction of
direction of the ball and interwined with each other to form flower‐like shapes at some surface areas.
the ball and interwined with each other to form flower-like shapes at some surface areas. With the
With the oxidation time prolonged to 5 h, large amounts of small nanosheets along the tangential
oxidation time prolonged to 5 h, large amounts of small nanosheets along the tangential direction of
the ball were visibly displayed, and some nanosheets debris also existed along the radial direction.
direction of the ball were visibly displayed, and some nanosheets debris also existed along the radial
direction. the
After oxidation
After that lasted
the oxidation for lasted
that 10h, thefor
Bi coatings
10h, the were oxidized were
Bi coatings adequately and formed
oxidized large and
adequately
staggered nanosheets along the radial direction of the ball. Elevating the temperature to 773 K resulted
formed large staggered nanosheets along the radial direction of the ball. Elevating the temperature
in completely different growth direction of Bi2 O3 crystals. Specifically, at the first oxidation stage,
to 773 K resulted in completely different growth direction of Bi 2O3 crystals. Specifically, at the first
the Bi2 O3 crystals appeared as irregular particles, which grew along the tangential direction of the ball.
oxidation stage, the Bi2O3 crystals appeared as irregular particles, which grew along the tangential
Then, nanosheets along the radial direction of the ball gradually occurred with the oxidation preserved
direction of the ball. Then, nanosheets along the radial direction of the ball gradually occurred with
for 5 h, and flower-like structure stacked by nanosheets were almost completely formed when the time
the oxidation
prolonged to preserved for 5 structure
10 h. The same h, and evolution
flower‐like structure
tendency stacked for
was observed by Bi
nanosheets were almost
2 O3 coatings sintered
completely formed when the time prolonged to 10 h.
at 873 K, except that larger polygonal Bi2 O3 crystals scattered fine nanoparticles on its surface were was
The same structure evolution tendency
observed for Bi
formed, and2O 3 coatings sintered at 873 K, except that larger polygonal Bi
much fewer nanosheets along the radial direction of the ball were observed, 2O3 crystals scattered
even when
fine nanoparticles on its surface were formed, and much fewer nanosheets along the radial direction
the time increased to 5 and 10 h. For Bi2 O3 coatings prepared at 973 K, much larger polygonal Bi2 O3
crystals similarly scattered fine nanoparticles always emerged along the tangential
of the ball were observed, even when the time increased to 5 and 10 h. For Bi 2Odirection of the ball
3 coatings prepared at
in spite of the oxidation duration of 10 h. Hence, from the structure evolution rules
973 K, much larger polygonal Bi2O3 crystals similarly scattered fine nanoparticles always emerged of Bi2 3 coatings,
O
it could be generally concluded that lower temperature apt to form radial growth structure with
along the tangential direction of the ball in spite of the oxidation duration of 10 h. Hence, from the
nanosheets was interlaced, and yet higher temperature apt to generate tangential growth structure
structure evolution rules of Bi 2O3 coatings, it could be generally concluded that lower temperature
consisted of irregular polygonal crystals and nanoparticles.
apt to form radial growth structure with nanosheets was interlaced, and yet higher temperature apt
to generate tangential growth structure consisted of irregular polygonal crystals and nanoparticles.
of the ball were observed, even when the time increased to 5 and 10 h. For Bi2O3 coatings prepared at
973 K, much larger polygonal Bi2O3 crystals similarly scattered fine nanoparticles always emerged
along the tangential direction of the ball in spite of the oxidation duration of 10 h. Hence, from the
structure evolution rules of Bi2O3 coatings, it could be generally concluded that lower temperature
apt to form radial growth structure with nanosheets was interlaced, and yet higher temperature apt
Coatings 2018, 8, 14 5 of 10
to generate tangential growth structure consisted of irregular polygonal crystals and nanoparticles.
Coatings 2018, 1, 14 5 of 10
(a)
Figure 3. Cont.
(b)
(c)
(d)
Figure 3. The surface morphologies of Bi
3. The surface morphologies of Bi 2O3 coatings: (a1) BC‐673‐2; (a2) BC‐673‐5; (a3)BC‐673‐10; (b1)
Figure 2 O3 coatings: (a1) BC-673-2; (a2) BC-673-5; (a3) BC-673-10;
BC‐773‐2; (b2) BC‐773‐5; (b3) BC‐773‐10; (c1) BC‐873‐2; (c2) BC‐873‐5; (c3) BC‐873‐10; (d1) BC‐973‐2;
(b1) BC-773-2; (b2) BC-773-5; (b3) BC-773-10; (c1) BC-873-2; (c2) BC-873-5; (c3) BC-873-10; (d1) BC-973-2;
(d2) BC‐973‐5; (d3) BC‐973‐10.
(d2) BC-973-5; (d3) BC-973-10.
3.3. Structure Evolution Mechanism
3.3. Structure Evolution Mechanism
Based on the above SEM images analysis, the structure evolution mechanism was deduced as
Based When
follows. on thethe above SEM images
Bi coatings analysis,at the
were oxidized structure
673 evolution
K, Bi and mechanism
O2 diffusion was deduced
first simultaneously
as occurred, resulting from sufficient O
follows. When the Bi coatings were oxidized at 673 K, Bi and O2 diffusion first simultaneously
2 around the coatings surface and active Bi element; then, with
occurred, resulting from sufficient O
time prolonged, O2 around the coatings
2 around the coatings
surface surface
decreased and and active Bi
therefore Bi element;
diffusion then, with time
dominated,
prolonged, O around the coatings
which led to overall radical growth of Bi
2 surface decreased and therefore Bi diffusion dominated,
2O3 crystals along the surface of Al2O3 ball. However, when which led
to temperature was elevated to 773, 873, and 973 K, the oxidation rates of Bi coatings were accelerated
overall radical growth of Bi2 O3 crystals along the surface of Al2 O3 ball. However, when temperature
was elevated
and the Bi2to
O3 773, 873, and
coatings 973
were K, the oxidation
relatively rates ofhindered
thicker, which Bi coatingsthe were accelerated
Bi diffusion and and the Bi
thereby O22O
3
diffusion
coatings weredominated
relatively the oxidation,
thicker, which leading
hinderedto thetangential growth
Bi diffusion of Bi2O3O
and thereby crystals.
2 diffusionWhen time
dominated
theincreased,
oxidation,O2leading
around tothe coatings’ growth
tangential surface ofdecreased. Thus, the
Bi2 O3 crystals. When oxidation was dominated
time increased, by Bi
O2 around the
diffusion and radical growth of Bi
coatings’ surface decreased. Thus, 2the O3 crystals emerged. The growth tendency of Bi
oxidation was dominated by Bi diffusion 2and O3 crystals on the
radical growth
of surface of Al
Bi2 O3 crystals2O3emerged.
ball with calcination time is briefly illustrated in Figure 4. Specifically, the irregular
The growth tendency of Bi2 O3 crystals on the surface of Al2 O3 ball with
crystals gradually
calcination time is brieflygrew larger along
illustrated the tangential
in Figure direction
4. Specifically, of the balls
the irregular with gradually
crystals the oxidation
grewtime
larger
extended
along and at appropriate
the tangential direction oftime;
the Bi 2O3 nanosheets along the radial of the balls appeared, which
balls with the oxidation time extended and at appropriate time;
Bi2continued to increase and completely spread over the whole surface of the balls. Thus, Bi
O3 nanosheets along the radial of the balls appeared, which continued to increase and 2O3 coatings
completely
with radial growth structure assembled by nanosheets could be easily realized at lower temperature
lasting for longer time, while those with tangential growth structure could be simply achieved by
controlling the temperature at higher level accompanied by relatively shorter oxidation time.
Coatings 2018, 8, 14 6 of 10
spread over the whole surface of the balls. Thus, Bi2 O3 coatings with radial growth structure assembled
by nanosheets could be easily realized at lower temperature lasting for longer time, while those with
tangential growth structure could be simply achieved by controlling the temperature at higher level
accompanied by relatively shorter oxidation time.
Coatings 2018, 1, 14 6 of 10
Coatings 2018, 1, 14 6 of 10
Figure 4. The growth tendency of Bi2O3 crystals on the surface of Al2O3 ball with calcination time increasing.
Figure 4. The growth tendency of Bi2 O3 crystals on the surface of Al2 O3 ball with calcination time increasing.
3.4. XPS
Figure 4. The growth tendency of Bi
3.4. XPS 2O3 crystals on the surface of Al2O3 ball with calcination time increasing.
The surface chemical composition and valence state of Bi element in BC‐873‐5 were investigated
by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious
The surface
3.4. XPS chemical composition and valence state of Bi element in BC-873-5 were investigated
peak. Figure 5a shows the XPS survey spectra of BC‐873‐5, in which Bi and O elements can be clearly
identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi element
by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious
The surface chemical composition and valence state of Bi element in BC‐873‐5 were investigated
(Figure 5b), two strong peaks located at 158.98 and 164.28 eV are assigned to Bi 4f7/2 and Bi 4f5/2,
peak.by XPS analysis, as illustrated in Figure 5. The binding energy was corrected by C 1s adventitious
Figurerespectively,
5a shows the is XPS
which survey with
in agreement spectra of BC-873-5,
the reported in which
values, indicating Bithe
Bi3+ in and O elements
coating. The can be
clearly identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi
binding energy of Bi 4f peaks in BC‐873‐5 shifted to a larger value compared
peak. Figure 5a shows the XPS survey spectra of BC‐873‐5, in which Bi and O elements can be clearly to BC‐873‐2 [23],
implying the local environment and electron density surrounding Bi cation changed with the
element (Figure 5b), two strong peaks located at 158.98 and 164.28 eV are assigned to Bi 4f 7/2 and
identified, confirming the formation of bismuth oxide. From the high resolution spectra of Bi element
oxidation further proceeding. Figure 5c presents the high‐resolution O 1s spectrum. The spectrum
(Figure
Bi 4f 5/2 5b), two strong
, respectively, whichpeaks is in located
agreement at 158.98
with and 164.28 eV values,
the reported are assigned to Bi 4fBi
indicating 3+ in the
7/2 and Bi 4fcoating.
5/2,
can be deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O 2− in Bi–O bonds, while
respectively,
that which
at 530.9 is
eV in
is agreement
characteristic with
of the
surface reported
hydroxyl values,
groups, indicating
which
The binding energy of Bi 4f peaks in BC-873-5 shifted to a larger value compared to BC-873-2 [23], is very Bi 3+ to
closed in the
the coating.
values The
binding reported in the literature [24,25].
energy of Bi 4f peaks
implying the local environment andin electron
BC‐873‐5 shifted surrounding
density to a larger value compared
Bi cation changed to with
BC‐873‐2 [23],
the oxidation
implying the local environment and electron density surrounding Bi cation changed with the
further proceeding. Figure 5c presents the high-resolution O 1s spectrum. The spectrum can be
oxidation further proceeding. Figure 5c presents the high‐resolution O 1s spectrum. The spectrum
deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O2 − in Bi–O bonds, while that
can be deconvoluted into two peaks. The peak at 529.7 eV is characteristic of O2− in Bi–O bonds, while
at 530.9 eV is characteristic of surface hydroxyl groups, which is very closed to
that at 530.9 eV is characteristic of surface hydroxyl groups, which is very closed to the values
the values reported in
the literature [24,25].
reported in the literature [24,25].
Figure 5. (a) XPS spectrum of BC‐873‐5; High‐resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC‐873‐5.
Figure 5. (a) XPS spectrum of BC‐873‐5; High‐resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC‐873‐5.
Figure 5. (a) XPS spectrum of BC-873-5; High-resolution XPS spectra of (b) Bi 4f and (c) O 1s in BC-873-5.
Coatings 2018, 8, 14 7 of 10
Coatings 2018, 1, 14 7 of 10
Figure 6. UV‐Vis diffuse reflectance spectra of the as‐prepared coatings: (a) BC‐673‐2, BC‐673‐5,
Figure 6. UV-Vis diffuse reflectance spectra of the as-prepared coatings: (a) BC-673-2, BC-673-5, BC-673-10,
BC‐673‐10, BC‐773‐2, BC‐773‐5, BC‐773‐10; (b) BC‐873‐2, BC‐873‐5, BC‐873‐10, BC‐973‐2, BC‐973‐5,
BC-773-2, BC-773-5, BC-773-10; (b) BC-873-2, BC-873-5, BC-873-10, BC-973-2, BC-973-5, BC-973-10.
BC‐973‐10.
29.93% of MG was degraded. Moreover, if no catalyst was added or no light used, the degradation
Coatings 2018, 1, 14
efficiencies of MG decreased to 14.66% and 6.3%, respectively, which confirmed the key role of 8 of 10
both
photocatalyst and light. Besides, the reaction rate constants of the samples for MG degradation were
photocatalyst and light. Besides, the reaction rate constants of the samples for MG degradation were
obtained according to the method described in the literature [23] and were summarized in Table 1.
obtained according to the method described in the literature [23] and were summarized in Table 1.
The reusability of the photocatalyst coating was also investigated by selecting BC-873-5 as the
The reusability of the photocatalyst coating was also investigated by selecting BC‐873‐5 as the
example. The repeated experimental results are shown in Figure 7c, from which it can be noticed that
example. The repeated experimental results are shown in Figure 7c, from which it can be noticed that
the photocatalytic activity of BC-873-5 reduced by a certain extent after three cycles, in spite of this,
the photocatalytic activity of BC‐873‐5 reduced by a certain extent after three cycles, in spite of this,
the degradation efficiency for MG was still maintained above 80%. These results evidently proved the
the degradation efficiency for MG was still maintained above 80%. These results evidently proved the
validity of the coating as excellent and easily recycled photocatalysts for organic dye degradation.
validity of the coating as excellent and easily recycled photocatalysts for organic dye degradation.
Figure 7. The degradation efficiencies of MG solution over the series of Bi2O3 photocatalyst coatings:
Figure 7. The degradation efficiencies of MG solution over the series of Bi2 O3 photocatalyst coatings:
(a) after irradiating for 180 min; (b) control experiment results; and (c) the reusability of BC‐873‐5.
(a) after irradiating for 180 min; (b) control experiment results; and (c) the reusability of BC-873-5.
Table 1. The reaction rate constants of the samples.
Table 1. The reaction rate constants of the samples.
Samples Rate Constants (min−1)
Samples
BC‐673‐2 0.0091 (min−1 )
Rate Constants
BC‐673‐5
BC-673-2 0.0115
0.0091
BC‐673‐10
BC-673-5 0.0109
0.0115
BC‐773‐2
BC-673-10 0.0092
0.0109
BC-773-2
BC‐773‐5 0.0092
0.0113
BC-773-5
BC‐773‐10 0.0113
0.0104
BC-773-10
BC‐873‐2 0.0104
0.0125
BC-873-2
BC‐873‐5 0.0125
0.0150
BC-873-5 0.0150
BC‐873‐10 0.0137
BC-873-10 0.0137
BC‐973‐2
BC-973-2 0.0109
0.0109
BC‐973‐5
BC-973-5 0.0125
0.0125
BC‐973‐10
BC-973-10 0.0117
0.0117
4. Conclusions
Bi2O3 photocatalyst coatings were developed via a ball milling followed by the thermal oxidation
method. Oxidation under different temperatures and times resulted in quite different compositions
and structures, which affected the related performances. The results showed that monoclinic Bi2O3
coatings were obtained at 673 or 773K for 2h, while oxidation at a higher temperature and a longer
Coatings 2018, 8, 14 9 of 10
4. Conclusions
Bi2 O3 photocatalyst coatings were developed via a ball milling followed by the thermal oxidation
method. Oxidation under different temperatures and times resulted in quite different compositions and
structures, which affected the related performances. The results showed that monoclinic Bi2 O3 coatings
were obtained at 673 or 773 K for 2 h, while oxidation at a higher temperature and a longer time resulted
in mixed-phase Bi2 O3 coatings. Moreover, Bi2 O3 coatings with radial growth structure assembled
by nanosheets could be easily realized at a lower temperature lasting for longer time, while those
with a tangential growth structure could be simply achieved by controlling the temperature at a
higher level accompanied by a relatively shorter oxidation time. Photo-degradation of malachite
green solution under simulated solar irradiation demonstrated that the developed coatings possessed
good photocatalytic activities and cycle performances. The easily recycled coatings provide a type of
visible-light-driven photocatalyst suitable for practical water treatment application.
Acknowledgments: This work is supported by the Youth Innovation Foundation of Tianjin University of Science
& Technology (No. 2015LG11), the Innovation Team Program of Tianjin University of Science & Technology
(No. 10117), and the National Nature Science Foundation of China (No. 51404170).
Author Contributions: Lijun Cheng conducted the experiments and was the lead author. Liang Hao was the
internal guider and Yun Lu was the external consultant.
Conflicts of Interest: The authors declare no conflict of interest.
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